Electrochemical sandwich aptasensor for the carcinoembryonic antigen using graphene quantum dots, gold nanoparticles and nitrogen doped graphene modified electrode and exploiting the peroxidase-mimicking activity of a G-quadruplex DNAzyme

A sandwich-type electrochemical aptasensor has been constructed and applied for sensitive and selective detection of the carcinoembryonic antigen (CEA). The surface of a glassy carbon electrode (GCE) was first modified with nitrogen-doped graphene and then gold nanoparticles and graphene quantum dots electrodeposited on it to obtain an architecture of type GQD/AuNP/NG/GCE. In the next step, the CEA-binding aptamer was immobilized on the modified GCE. Hemin intercalates in the amino-modified hemin aptamer to form a hemin-G-quadruplex (hemin-G4) DNAzyme. The amino modified CEA aptamer II is connected to hemin-G4 by glutaraldehyde (GA) as a linker to produce CEAaptamerII/GA/hemin-G4 (=ApII/GA/DNAzyme). Through a sandwich mode, the ApII/GA/DNAzyme bioconjugates are captured on the modified GCE. Subsequently, the hemin-G4 acts as peroxidase-mimicking DNAzyme and rapidly catalyzes the electroreduction of hydrogen peroxide. The quantitative determination of CEA was achieved by differential pulse voltammetry, best at a working potential of around -0.27V vs. Ag/AgCl. Under optimized conditions, the assay has a linear response in the 10.0fgmL(-1) to 200.0ngmL(-1) CEA concentration range and a lower detection limit of 3.2fgmL(-1).